Color photographic material comprising a blue-green color coupler

ABSTRACT

A blue-green color coupler comprising a 1-hydroxy-2-benzoyl or naphthoyl amino-substituted acid wherein the amino group is attached to the ring-attached carbonyl group through one or more amino acids, and color-photographic material comprising said coupler.

United States Patent Credner et al.

[451 Apr. 25, 1972 [54] COLOR PHOTOGRAPHIC MATERIAL COMPRISING ABLUE-GREEN COLOR COUPLER [72] Inventors; Hans-Heinrich Credner, 'Munich;Hans Glockner, Pullach; Fritz Muller, Munich;

Friedrich Wilhelm Kunitz, Leverkusen, all of Germany AGFA-GevaertAktiengesellschaft, Leverkusen, Germany [22] Filed: Nov. 18,1968

[21] Appl.No.: 776,747

[73] Assignee:

[30] Foreign Application Priority Data Nov. 18, 1967 Germany ..P 15 97499.9

[52] US. Cl ..96/74, 96/100, 260/144, 260/505 R, 260/558 R [51] Int. Cl..G03c 1/40 [58] Field of Search ..96/100, 74

Primary Examiner-William D. Martin Assistant Examiner-Ralph HusackAtt0rney-Michael S. Striker [57] ABSTRACT A blue-green color couplercomprising a l-hydroxy-Z-benzoyl or -naphthoyl amino-substituted acidwherein the amino group is attached to the ring-attached carbonyl groupthrough one or more amino acids, and color-photographic materialcomprising said coupler.

16 Claims, No Drawings COLOR PHOTOGRAPHIC MATERIAL COMPRISING ABLUE-GREEN COLOR COUPLER BACKGROUND OF THE INVENTION The inventionrelates to a blue-green component for photographic color materials. Dyesformed by reaction with a developer in photographic material must meetspecific optical requirements. Ideally, a blue-green color-forming agentshould absorb red light completely and should transmit as.

much as possible of the green and blue light. A color-forming agent alsoshould provide for high color densities.

Apart from the optical properties, the dyes must meet high requirementsregarding hydrolytic stability and light fastness. In addition, a colorcoupler must be easy to disperse andlmust' give a homogeneous dispersedcolor grain and a good coupling speed.

As couplers for blue-green, naphthols are particularly suitable,preferably the condensation products of aliphatic, aromatic orheterocyclic amines with l-hydroxy-2-naphthoic acids or derivativesthereof, yet many of the conventional blue-green couplers will yielddyes which do not meet all requirements.

SUMMARY OF THE INVENTION More specifically, the compounds of theinvention have theformula wherein R and R are the same or differentandare hydrogen, alkyl, cycloalkyl, or halogen, or wherein R and R togetherand with the adjoining carbon atoms of the phenol ring form a fusedbenzene ring or a fused cycloalkyl ring; R is hydrogen or a Z-equivalentcoupler substituent; R is hydrogen,alkyl or aralkyl; R is alkyl,aralkyl, aryl, aryl substituted by alkyl, halogen or alkoxy; and Ama isat least one amino acid residue.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the above formulatedcompounds of the invention, the alkyl group both in alkyl and inalkyl-substituted radicals preferably comprises between eight and 22carbon atoms. This applies specifically to the radicals identified as RR R and R The Z-equivalent coupler substituents which'may formtheradical identified as R preferably are chlorine or a sulfo- 'orsubstituted phenylazogroup such as acetyl-substituted phenylazo. Thearyl in R may be unsubstituted or may be substituted by alkyl, halogen,or alkoxy. Thealkyl group both when standing by itself and as part ofalkoxy preferably has from eight to 22 carbon atoms.

The amino acid residue identified-as Ama may be a single amino acidresidue or a peptide chain suchas a dipeptide. The amino acid from whichthe residue is derived, e.-g., may have from two to 12 carbon atoms and,for instance, may be glycine, alanine, phenylalanine, valine, leucine,serine, 4- amino-butyric acid, or amino-caproic acid. The dipeptide may,for instance, be glycylglycine. The nitrogen atom in these amino acidswhich in the molecule is attached to the carbonyl group of the main ringmay in turn be substituted, for instance, by alkyl or aryl. Alkyl inthis case should preferably again have from eight to 22 carbon atoms andaryl should preferably be phenyl.

The following formulas illustrate some of the compounds coming under thegeneral formula:

I CONHCHZC ONHCmHz;

| CH3 1 CONHOHCONHCuHea c oNmiHcoNricutts I @oouncmcmo ONHCnHu V e on1aH|1 @oormomcmoon OomwcmomcormGsmm 8 omomoomi .@-con 5 I C "H20 OH O0ON/ CHzC H O ONHCH C ONHO H CONHCHzCHzC HzCONHCuHn I OCrul-Iaa C ONHCIIC ONHCwHn OH H: mp, CONHCHZCONHCNHQ; H1

O ONHCH2C ONHCmHn l sour 15 m -ooNHcH,oH.ooNH

l uHzu l 000cm The following is a compilation of the melting points ofsome of the intermediate products. The ethyl esters are compounds withgood crystallizing properties which can be obtained with a high degreeof purity by recrystallization from ethanol. The saponification iseffected in 5 N glacial acetic acid with 5 N hydrochloric acid. Thesynthesis of the phenyl esters is effected, for instance, be preparing abenzene-type suspension with phosphorus oxytrichloride and thusaccomplishing complete solution. The chemical structure of the newcompounds was confirmed by checking the mass spectra:

TABLE I.INTERMEDIATES CQNHCHqCO 5 CONIICH:CO 11 TABLE I Continued CONThe compounds of the invention may be made by proceeding through thearoyl amino acids. The alkyl esters of amino acids are first condensedwith the phenyl esters of aromatic carboxylic acids. The aroyl aminoacidalkylesters are then subjected to saponification and the reactionproduct is then caused to react with the desired amine. This aminationreaction may be effected by means of a phosphorazo reaction, or thecompound in the form of its phenyl ester may be reacted in a salol melt.The latter method results in a higher yield and particularly pure finalproducts.

The following examples illustrate the manner of making the compoundsshown above as Nos. 1, 6, and 9.

EXAMPLE 1 This Example relates to the compound listed above as No. l.The reaction proceeds as follows:

a. l-hydroxy-naphthoyl-Z-glycineethylester:

200 g glycineethylester and 400 g l-hydroxynaphthoic acid- 2-phenylesterwere heated in an oil bath in a round flask provided with a riser to Cfor 5 hours. The phenol which split off was then removed by distillingit off in vacuum and the melt was poured into ethanol and caused tocrystallize. The crude product was recystallized from ethanol.

M.p. 13 1 C, yield: 300 g.

b. l-hydroxy-naphthoyl-2-glycine:

100 g of the ester obtained in Step (a) were dissolved in 700 ml glacialacetic acid and were maintained with 500 ml 5 N hydrochloric acid in aboiling-water bath for 40 minutes. The solution was poured into 3 Iwater and the precipitated product was removed by suction, washedneutral, dried and boiled with a high boiling-point gasoline.

M.p.: 204 C, yield: 77.2 g, which corresponds to 86 percent of thetheoretical yield.

c. l-hydroxy-naphthoyl-2-glycinephenylester:

50 g ofthe acid, that is 0.205 mol, obtained in Step (b) were subjectedto stirring with 38.4 g (0.41 mol) phenol and 61.5 ml (0.205 mol)phosphorus oxytrichloride in 500 ml dry benzene for 5 hours upon refluxuntil complete solution was obtained. The resulting solution was washedwith water, treated with a 3 percent sodium carbonate solution, washedneutral with water, dried, and concentrated by evaporation. The residuewas recrystallized from a high boiling point gasoline.

M.p.: 138 C, yield: 32.] g 49 percent of the theoretical yield.

d. l-hydroxy-naphthoyl-Z-gIycine-octadecylamide:

32.1 g of the phenylether, that is 0.1 mol, formed in the previous step,were heated together with 259 g (0.2 mol) octadecylamine to l50 C in avacuum and the phenol that split off was removed by distillation. Themelted mass was then poured into mechanol and caused to crystallize. Itwas recrystallized thereupon from ethanol.

M.P.: 126 C, yield: 35 g, which corresponds to 70 percent of thetheoretical yield.

EXAMPLE 2 This example relates to the coupler of which the formula wasshown above as No. 6. The process was again carried out in steps whichwere as follows:

(a) B-alanineethylester:

178 g B-alanine were heated with 1,000 ml ethanol and 150 g sulfuricacid for 18 hours upon reflux. The alcohol was removed by distillationand the residue was reacted with 400 ml ether. Ammonia was thenintroduced for minutes-and the ether was thereupon removed by decanting.The residue was again reacted with ether and this procedure was repeatedfive times. The combined ether fractions were'dried with sodium sulfateand subjected to concentration by evaporation. The residue wasfractionated. The main fraction boiled at 60 C (at 3-4 mm Hg).

Yield: 155 g, corresponding to 66 percent of the theoretical yield.

b. l-hydroxy-naphthoyl-2-alanineethylester:

155 g fl-alanineethylester and 264 g naphthsalol were con-' densed in amanner analogous to Example 1 and were precipitated in methanol. Atwo-fold recrystallization from methanol yielded 145 ghydroxy-naphthoyl-alanine-ester; m.p. 93-94 C.

c. l-hydroxy-naphthoyl-2-alanine naphthoyl-Z-alaninephenylester:

Again obtained in a manner analogous to thatdescribedin Example 1. Themelting points of these esters are listed in the above table relatingtothe Intermediate Products.

d. l-hydroxy-naphthoyl-2-alanineoctadecy1amide:

33.5 g (0.1 mol) of the thus formed phenyl ester were heated to 150 C ina vacuum with 26.9 g (0.1 mol) octadecylamine. The phenol that split offwas removed by distil lation and the fused mass was precipitated inmethanol. Recrystallization from alcohol followed.

M.p.: 90-91 C, yield: 31 g, which corresponds to 60 percent of thetheoretical yield.

and l-hydroxy- EXAMPLE 3 This example relates to the coupler listedabove as No. 9. The making of the ester was carried out in the followingsteps:

a. N-phenylalanineethylester:

181 g B-bromopropionic acid-ethylester (1 mol) and 186 g (2 mols)aniline were maintained at 80 C upon stirring for 1 hour. The reactionwas neutralized with a 5 percent sodium carbonate solution and theproduct was taken up' in chloroform. After removing the solvent, 136 gN-phenylalanineethylester were obtained by fractionaldistillation atl28134 C (0.2 torr). This corresponded to' a yield of 70 percent of thetheoretical value.

b. 1-hydroxynaphthoyl-2-N-phenylalanine-ethylester:

136 g (0.7 mol) N-phenylalanineethylester and 132 g (0.5 mol)naphthsalol were maintained at 140 C for 3 hours. The phenol was thendistilled off in a vacuum and the fusedmass was poured into methanol.Recrystallization was effected twice from methanol.

M.p.: 9899 C, yield: 109 g, corresponding to 60'percent of thetheoretical yield.

c 1-hydroxy-naphthoyl-2N-phenylalanine:

The saponiiication was effected as in Example 1. The product obtainedhad a melting point of 150 C. The yield corresponded to 85 percent ofthe theoretical yield.

(1. 1-hydroxy-naphthoyl-2-N-phenylalanine-2-tetradecylhydroxyanilide:

30.5 g Z-tetradecylhydroxyaniline (0.2 mol) were dissolved in 500 mlabs. pyridine. 4.4 cc (0.05 mol) phosphorus oxytrichloride were added at0 C and the solution was subjected to stirring for 3 hours. 33.5 g (0.1mol) of the acid were then added and the reaction mixture was heated for4 hours upon reflux. It was precipitated over ice-hydrochloric acid. Theprecipitate was removed by suction, washed with water and dried.Recrystallization was effected from alcohol.

M.p.: 86-88 C, yield: 43 g, which corresponds to 69 percent of thetheoretical yield.

The couplers of the invention can also be made other than by synthesisalong the route of the aroylamino-acids, for instance in conventionalmanner by condensing l-hydroxynaphthoic acid-phenylester with thecorresponding amine, such as 6-aminocaproicacid-2-hexadecylhydroxyanilide (cou- THE PHOTOGRAPHIC EMULSIONS The newcouplers can be incorporated in a photographic emulsion by dissolvingthem in an aceticester and dispersing them in a gelatin solution to theextent that they are hydrophobic. If they are hydrophilic, that is ifthey include acid groups,

they must be employed in an alkaline solution. As the vehicle or bindingagent for the solution, gelatin is preferred. However, other vehiclesmay also be used. The emulsion is then applied to a support, forinstance of glass, cellulose acetate, polyester film, or papercontaining a barite filler. The emulsion may be applied to the supportas a single coat, or it may be applied as part of several silver halideemulsions which contain the couplers for the other primary colors.

The new couplers are superior in many respects to the prior artproducts. Most of the blue-green couplers of the invention whendeveloped result in distinctly higher color densities than obtainablewith known coupling compounds. The dyes thus formed are of a highbrilliancy, since the densities of the adjacent (secondary) colors arelower. Some of the compounds of the invention result in photographicdyes which are absolutely stable against hydrolysis.

The following examples illustrate the making of the photographicmaterial EXAMPLE 4 Two g of the coupler listed above as No. l weredissolved in 10 ml acetic acid ester and dispersed with a 50 ml 5percent gelatin solution which contained 4 ml of a 10 percent sodiumdodecylbenzenesulfonate. The dispersion was added to a photographicsilver halide emulsion and was then cast on a support, subjected toexposure and developed in a bath containing2-amino-5-diethylaminotoluene as color-developing agent. In reversaldevelopment, a blue-green color image was obtained having an absorptionmaximum of 652 nm.

The following table shows the color density, the percentage secondaryabsorption in the blue and green spectral range (measured with aMacbeth-Anscodensitometer) and the percentage loss of color density in ahigh humidity oven (28 days, 60" C, 96 percent relative air humidity).In addition, data are furnished for comparison pertaining to twogenerally accepted high-quality couplers, i.e. (l)l-hydroxy-2-N-octadecylnaphthamide and (II)1-hydroxy-(2',4'-diamylphenoxy-butyl)-2-naphthamide (U.S. Pat. No.2,474,293):

TABLE II Loss of Density Absorption in High Coupler D max blue greenHumidity Oven No. l 1.92 24 18 1 7: Control 1 1.64 31 22 13 7!. Control11 1.33 31 20 14 7a EXAMPLE 5 2.5 g of Coupler No. 9 were dissolved in 8ml acetic acid ester and dispersed with 50 m1 of a 5 percent gelatinsolution containing 4 ml of 10 percent sodium-dodecylbenzenesulfonate.The dispersion was added to a photographic emulsion and cast, as inExample 1, then subjected to exposure and development.

The following Table shows the absorption maxima of the blue-greendyestuffs formed with different developers by negativeandreversalprocess, and shows the color density of the dyes after storing for l and28 days in a high humidity oven at 60 C and 96 percent relativehumidity, and employing the emulsion of this example:

TABLE III N egntivo color Rovursul color density density Max. Max.Developing agent (nm) Before After l (mu) Before After N, N-diethyl-p-phenylenedlamine 631 1. 52 1. 50 635 1. 84 1. 79 2-amno-dietliyl-arninotoluene 650 0. 73 0. 71 648 l. 40 1. 362-um1no-5-N-ethyl-N-methylsulfonarnidoethyl-tolueue 646 0. 94 0. 95 6440. 49 0. 48 N-butyl-N-sulfobutyI-p-phenylenediamine (paper developer)640 1.17 1. 17

1 After 1 day in high humidity oven. 2 After 28 days in high humidityoven.

What is claimed as new and desired to be protected by Letters Patent isset forth in the appended claims:

1. A color-photographic material comprising a support, a blue-greendiffusion-proof color coupler compound, and at least one photographicsilver halide emulsion applied to said support, said emulsion containingsaid color coupler and said color coupler consisting essentially of acompound of the formula wherein R and R are the same or different andare hydrogen, alkyl, cycloalkyl or halogen, or wherein R and R togetherwith the adjoining carbon atoms of the phenol ring form a fused benzenering or a fused cycloalkyl ring, R is hydrogen or a 2-equivalent couplersibstituent, R is hydrogen, alkyl or aralkyl, R is alkyl, aralkyl, arylor substituted aryl, and Arna is at least one amino acid residue or asubstituted amino acid residue.

2. The material of claim 1 wherein the alkyl group in alkyl, uralkyl andalkoxy of R,, R R and R has from eight to 22 carbon atoms.

3. The material of claim 1 wherein the 2-equivalent substituent in R ischlorine, a sulfogroup, phenylazo or s substituted phenylazo.

4. The material of claim 3 wherein the phenylazo group of R issubstituted in the phenol ring by a methyl-benzoate group.

5. The material of claim 1 wherein the amino acid residue has from twoto 12 carbon atoms.

6. The material of claim 1 wherein the amino acid residue is substitutedin the amino group by phenyl.

7. The material of claim 1 wherein the amino acid residue is formed byan acid selected from the group consisting of glycine, a-alanine,B-alanine, phenyl-alanine, valine, leucine, serine, 4-amino-butyric acidand o-amino-caproic acid.

8. The material of claim 1 wherein the amino acid residue is a peptideresidue.

9. The material of claim 8 wherein the peptide is a dipeptide.

10. The material of claim 9 wherein the dipeptide is glycylglycine.

11. The material of claim 1, the compound having the formula O ONHCH CONHC H 12. The material of claim 1, the compound having the formulaCONHCILCONHC H 13. The material of claim 1, the compound having the for-0 mula C ONHCHzCONHCnHn 14. The material of claim 1, the compound havingthe formula CONHCHaCHzCONI-IQ COOCH:

15. The material of claim 1, the compound having the formula OH Icmcmcorm CON 4) I u n as I 16. The color-photographic material of claim1 wherein a plurality of silver halide emulsions is superposed on saidsupport, one of the emulsions containing said coupler compound and atleast one other emulsion containing the coupler compound for anotherprimary color component.

2. The material of claim 1 wherein the alkyl group in alkyl, aralkyl andalkoxy of R1, R2, R4, and R5 has from eight to 22 carbon atoms.
 3. Thematerial of claim 1 wherein the 2-equivalent substituent in R3 ischlorine, a sulfo- group, phenylazo or s substituted phenylazo.
 4. Thematerial of claim 3 wherein the phenylazo group of R3 is substituted inthe phenol ring by a methyl-benzoate group.
 5. The material of claim 1wherein the amino acid residue has from two to 12 carbon atoms.
 6. Thematerial of claim 1 wherein the amino acid residue is substituted in theamino group by phenyl.
 7. The material of claim 1 wherein the amino acidresidue is formed by an acid selected from the group consisting ofglycine, Alpha -alanine, Beta -alanine, phenyl-alanine, valine, leucine,serine, 4-amino-butyric acid and 6-amino-caproic acid.
 8. The materialof claim 1 wherein the amino acid residue is a peptide residue.
 9. Thematerial of claim 8 wherein the peptide is a dipeptide.
 10. The materialof claim 9 wherein the dipeptide is glycylglycine.
 11. The material ofclaim 1, the compound having the formula
 12. The material of claim 1,the compound having the formula
 13. The material of claim 1, thecompound having the formula
 14. The material of claim 1, the compoundhaving the formula
 15. The material of claim 1, the compound having theformula
 16. The color-photographic material of claim 1 wherein aplurality of silver halide emulsions is superposed on said support, oneof the emulsions containing said coupler compound and at least one otheremulsion containing the coupler Compound for another primary colorcomponent.